Treatment of fibrous material and product resulting therefrom



Patented Oct. 2, 1951 TREATMENT OF FIBROUS MATERIAL AND PRODUCTRESULTING THEREFROM John W. Schick, Camden, and Howard D.

Hartough, Pitman, N. J., assignors to .Socony- Vacuum Oil Company,Incorporated, a corporation of New York No Drawing. ApplicationSeptember 4, 1947, Serial No. 712,214

As used herein, the term fibrous textile materials includes wool,cotton, linen, silk, rayon, nylon, hemp, into and various artificialfibers of organic material in the form of threads, skeins, or in wovenform and also paper, sheeted cellulose, leather, fur and the like.Furthermore, as used herein, the term "phenol includes monohydric andpolyhydric monocyclic phenols, alkylmonohydric phenols, alkylpolyhydricphenols, and monoand polyhydric polycyclic phenols.

In the co-pending application for United States Letters Patent SerialNo. 670,031, filed May 15, 1946, in the names of Howard D. Hartough andEverett H. Murray the preparation of novel nitrogenous resins isdescribed. This description teaches that such resins can be prepared byreacting (A) a compound having-at least one nuclear hydrogen atom ofpronounced reactivity, (B) an aldehyde and. (C) hydroxylaminehydrohalide and particularly (A) thiophene, (B) formaldehyde and (C)hydroxylamine hydrochloride in the ratio of about 0.5 to about 1 mole ofA: about 0.5 to about 2 moles of B: about 0.5 to about 1 mole of C attemperatures of about 10 C. to the reflux temperature. Furthermore inthe co-pending application for United States Letters Patent Serial No.772,212, filed September 4, 1947, in the names of John W. Schick andHoward D. Hartough, now Patent No. 2,546,946, the preparation ofmodified phenol-formaldehyde resins is described. According to thisdescription (A) a phenol devoid of reactive acidic and basic substituentand having at least one nuclear hydrogen atom of pronounced reactivity,(B) formaldehyde and (C) an ammonium halide are reacted in molal ratioof A:B:C=l: at least 3: more than 0.25 in the presence of an acid havinga dissociation constant above 1 10- but not greater than about 1.7 Inthe co-pending application for United States Letters Patent Serial No.

636,511, filed December 21, 1945, now abandoned, in the names of HowardD. Hartough and Sigmund J. Lukasiewicz, the preparation of nitrogenouscondensation products having as a characterizing group the thiopheneresidue, C-iHnS where n equals zero to 3 is described. This methodcomprises condensing at temperatures of about 65 C. to the refluxtemperature (A) a thiophene compound having at least one re- 7 Claims.(Cl. 117-76) placeable nuclear hydrogen atom selected from the groupconsisting of thiophene and thiophene having a stable electropcsitivenuclear substituent, (B) formaldehyde and (C) a nitrogenous compoundselected from the group consisting of chlorides and bromides of ammonia,primary amines, secondary amines, primary diamines and urea, saidthiophene compound, formaldehyde and nitrogenous compound being presentin the reaction mixture in the molal ratio of 1 to 220.5 to 4:025 to 3.In the co-pending application for United States Letters Patent SerialNo. 781,754, filed October 23, 1947, in the names of John W. Schick andHoward D. Hartough, the preparation of novel nitrogenous resinscontaining at least one 5-membered heterocyclic radical per polymer unitis described. The method therein described comprises reacting (A) a 5-membered heterocyclic compound having at least one nuclear hydrogen atomof pronounced reactivity, (B) formaldehyde and (C) a hydrohalide of oneof the group consisting of ammonia, alkyl substituted ammonia andhydroxyl substituted ammonia in the molal ratio of A:B:C=1:0.8-4:0.5-1.In the co-pending application Serial No. 772,213, filed September 4,1947 in the names of John W. Schick and Howard D. Hartough, a method ofpreparing emulsions of nitrogenous phenolic type resins is described.This method comprises condensing a phenol, an aldehyde and a hydrohalideof ammonia or substituted ammonia in the molal proportion ofphenol:aldehyde:hydrohalide of 1:1 to more than 1:05 to 5 in thepresence of sulfur dioxide or an alkali metal bisulfite.

It now has been discovered that the novel nitrogenous phenolic resinsdescribed in the pertinent foregoing applications and the novelnitrogenous heterocyclic resins described in the pertinent foregoingapplications can be used cooperatively in the treatment of fibroustextile materials to provide materials which are crushresistant andwater-proofed.

The method of crush-proofing and waterproofing fibrous textile materialscomprises preparing a water-soluble or water-suspendible nitrogenousresin of the phenol-aldehyde type as described in the aforesaidcopending applications, impregnating the textile material therewith,converting the water-soluble or water-dispersible resin to awater-insoluble form, heatcuring the resin, impregnating the textileassociated with the phenolic resin with a watersoluble derivative of anitrogenous heterocyclic resin, converting the water-soluble derivativeof the nitrogenous heterocyclic resin to the waterinsoluble form andheat-curing the water-insoluble nitrogenous heterocyclic resin.

A modification of the foregoing comprises impregnating textile materialwith a water-soluble or water-dispersible nitrogenous phenolic resin,impregnating the so-treated textile material with a water-solublederivative of a nitrogenous heterocyclic resin, converting thewatersoluble or water-dispersible forms of both resinous materials towater-insoluble forms and heat-curing the so-treated textile material.

Illustrative of the specific steps of a sequence which has providedsatisfactory results is the following:

About to parts by weight of a nitrogenous phenolic resin obtained asdescribed in the pertinent copending applications enumeratedhereinbefore is warmed in about 100 parts by weight of water or amixture of water and a cosolvent such as alcohol, acetone, etc. Theamount of co-solvent is that required to carry the resin intosuspension. The fibrous textile material to be treated is immersed inthe said suspension, the excess solution squeezed out and theimpregnated cloth immersed in an aqueous 12 weight per cent formaldehydesolution, again gently squeezed to remove excess formaldehyde solutionand cured at about 115 to 120 degrees centigrade. The so-treated textilematerial is then immersed in a 3 to weight per cent aqueous solution ofa water-soluble derivative of a nitrogenous heterocyclic resin, excesssolution removed and the water-soluble derivative converted to awater-insoluble derivative of the heterocyclic resin. The so-treatedtextile material is water-washed to remove loosely bound resinousmaterial on the surface and immersed in an alkaline aqueous formaldehydesolution. A 5 to 25 weight per cent solution is preferred. Thereafterthe textile material associated with both phenolic and heterocyclicnitrogenous resins is heat-cured at about 110 to about 125 degreescentigrade for a short time. The treated textile is then laundered andpressed to produce a crush-proofed and water-proofed textile.

Illustrative of the foreoing are the following non-limiting examples:

Example I A seven inch square of cotton poplin was im pregnated in anaqueous 10 weight per cent dispersion of a nitrogenous resin preparedfrom one mole of phenol, 3 moles of formaldehyde, one mole of ammoniumchloride and one mole of sodium bisulfite as described in the copendingapplication. Excess resin dispersion was removed and the impregnatedcloth immersed in an aqueous 12 weight per cent formaldehyde solution.Excess formaldehyde solution was removed and the impregnated poplinheat-cured at 115 to 120 degrees centigrade. The poplin associated withthe heat-cured phenolic resin was immersed in an aqueous solutioncontaining 6 weight per cent of active ingredient, the active ingredientbeing water-soluble derivative of a heterocyclic nitrogenous resin (thehydrochloride) prepared from one mole of thiophene, a large excess offormaldehyde, one mole of ammonium chloride and one mole of sodiumbisulfite. The poplin associated with heat-cured phenolic resin andwater-soluble derivative of the nitrogenous thiophene resin was immersedin an aqueous solution containing 10 weight per 4 with heat-curedphenolic resin and a water-insoluble form of the nitrogenous thiopheneresin was rinsed in cold water and immersed in an alkaline aqueoussolution of formaldehyde containing 12 weight per cent of formaldehydeand one weight per cent of sodium hydroxide. Thereafter the so-treatedpoplin was again heatcured at about 115 to 120 degrees centigrade. Aftertwo hand washings the treated poplin had a spray rating of and acrush-resistant finish.

Example If About 2 moles of thiophene, about 4 moles of ammoniumchloride, about 9 moles of formaldehyde as an aqueous solution thereofand about 0.8 mole of sodium bisulfite were heated at about 70 degreescentigrade for about 20 minutes. To the mixture was added a solution ofabout 0.5 mole of phenol in about 0.5 mole of thiophene. The resultantmixture was heated at reflux for about 2 hours. All of the material wasthen water-soluble. One part of the solution was diluted with 5 parts ofwater and cotton poplin impregnated therewith and heat-cured at about115 degrees centigrade. The poplin associated with the cured resinousmaterial was water-repellent and had a spray rating of about 70+ but wasnot crush-proof.

Example III A mixture of about 0.5 mole of phenol, about 0.5 mole ofthiophene, about one mole of ammonium chloride, about one mole of sodiumbisulflte and about 3 moles of formaldehyde as a 36 weight per centaqueous solution were heated about 4.5 hours. The temperature rose from'73 to about degrees centigrade. when the reaction cooled to ambienttemperature it separated into an upper orange colored layer and a loweryellow colored layer.

Ten grams of the upper resinous layer was suspended in 90 grams of waterand filtered. A seven inch square of cotton poplin was impregnated withthe solution, then immersed in aqueous 10 per cent sodium acetate,rinsed in cold water, immersed in a 12 per cent aqueous alkalineformaldehyde solution containing 1 per cent of sodium hydroxide andcured at to degrees centigrade. After three hand washings the so-treatedpoplin had a spray rating of 50 and some crease-resistant properties.

We claim:

1. A method of crush-proofing and waterproofing flbrous organic textilematerial which comprises immersing an organic textile material in anaqueous bath having dispersed therein about 10 to about 15 parts byweight of a nitro genous phenolic resin per 100 parts by weight ofaqueous medium, immersing said organic textile material in an aqueous 12weight per cent formaldehyde solution, heating said organic textilematerial and said resin at about 115 to about 120 C., immersing theso-treated organic textile material in an aqueous about 3 to about 25weight per cent solution of a nitrogenous heterocyclic resin, immersingthe so-treated organic textile material in an alkaline aqueous solutioncontaining about 5 to about 25 weight per cent formaldehyde, heating theso-treated organic textile material at about 110 to about C. and washingthe so-treated organic material; said nitrogenous phenolic resin havingbeen prepared by reacting (A) a phenol, (B) formaldecent of sodiumacetate. The poplin associated. N hyde and, C) a hal d selected from thegroup consisting of hydrohalides of ammonia and substituted ammonia inthe molal ratio of A:B:C=1:2-4:0.5-1; and said nitrogenousheterocyclicresin having been prepared by reacting (X) a compound having at leastone nuclear hydrogen atom of pronounced reactivity selected from thegroup consisting of thiophenes, furans and Dyrroles, (Y) formaldehydeand (Z) a halide selected from the group consisting of halide of ammoniaand substituted ammonia in the molal ratio of 1 to 2:0.5 to 4:0.25 to 3.

2. A method of crush-proofing and waterproofing fibrous organic textilematerial which comprises immersing an organic textile material in anaqueous dispersion of a nitrogenous phenolic resin, immersing theso-treated organic textile material in an aqueous bath containingformaldehyde, heating the so-treated organic textile material at about115 to 120 0.. immersing the so-treated organic textile material inaqueous solution containing a water soluble heterocyclic resin,immersing the so-treated organic textile material in an aqueous solutionof sodium acetate, immersing the so-treated organic textile material inan alkaline aqueous solution of formaldehyde, heating the sotreatedorganic textile material at about 115 to about 120 C., and washing theso-treated organic material; said nitrogenous phenolic resin having beenprepared by reacting (A) phenol, (B) formaldehyde, (C) ammonium chlorideand (D) sodium bisulnte in the molal ratio of A:B:C:D=1:3:1:1 and saidheterocyclic resin having been prepared by reacting (W) a thiophenehaving at least one nuclear hydrogen atom of pronounced reactivity, (X)formaldehyde, (Y) ammonium chloride and (Z) sodium bisulfite in themolal ratio of W:X:Y:Z=1: a large excess of 1 mole:1:1.

3. Aimethod of crush-proofing and waterproofing fibrous organic textilematerial which comprises contacting ,organic' textile material with anaqueous bath containing a nitrogenous phenolic resin, contacting theso-treated organic textile material with formaldehyde to convert saidresin to water-insoluble form, heating the so-treated organic textilematerial at elevated temperatures not greater than about 120 0.,contacting the so-treated organic textile material with an aqueous bathcontaining a watersoluble form of a nitrogenous heterocyclic resin.

' contacting the so-treated organic material with aqueous solution ofsodium acetate to convert said water-soluble form of said resin to awater-' insoluble form, heating the so-treated organic textile materialat elevated temperatures not greater than about 125 C., and washing theso-treated organic textile material; said nitrogenous phenol resinhaving been prepared by reacting (A) a phenol, (B) formaldehyde and (C)a halide selected from the group consisting of hydrohalides of ammoniaand substituted ammonia in the molal ratio of A:B:C== 1:24:0.5-1 andsaid nitrogenous heterocyclic resin having been prepared by reacting (X)a compound having at least one nuclear hydrogen atom ofpronouncedreactivity selected from the group consisting of thiophenes, furans andpyrroles, (Y) formaldehyde and (Z) a halide selected from the groupconsisting of halides oi ammonia and of substituted ammonia in the molalratio of X:Y:Z=1:0.8 to 4:0.5 to 1.

4. A method of crush-proofing and waterproofing ilbrous organic textilematerial which comprises contacting fibrous organic textile materialwith an aqueous bath containing a nitrogenous phenolic resin, contactingthe so-treated textile material with an aqueous bath containing anitrogenous heterocyclic resin, contacting said textile material,phenolic resin and heterocyclic resin with aqueous sodium acetate toconvertsaid resins to water-insoluble form, heating said textilematerial and said resins at elevated temperatures not greater than about125 C., and washing the so-treated organic textile material; saidnitrogenous phenolic resin having been v prepared by reacting (A) aphenol, (B) formaldehyde and (C) a halide selected from the groupconsisting of hydrohalides of ammonia and substituted ammonia in themolal ratio of A:B:C=l:2-4:0.5-1, and said nitrogenous heterocyclicresin having been prepared by reacting,(X) a compound selected from thegroup consisting of thiophene, furan and pyrrole, (Y) ,formaldehyde and(Z) a halide selected from-the group consisting of hydrohalide ofammonia and substituted ammonia, X and Z being in the molal ratio of 1:1and Y being present in excess of one mole per mole of X.

5. Fibrous organic textile material having distributed thereon anitrogenous phenolic resin prepared by reacting (A) a phenol, (B)formaldehjzde and (C) a halide selected from the group consisting of thehalides of ammonia and substituted ammonia in the molal ratio of A:B":C=1:2-4:0.5-1 and a nitrogenous hetero cyclic resin prepared byreacting (X) a heterocyclic compound selected from the group consistingof thiophene, furan. pyrrole, (Y) formaldehyde and (Z) a halide selectedfrom the group consisting of halides of ammonia and substituted ammonia,X and Z being in the molal ratio of 1:1 and Y being present in excess ofone mole per mole of x.

6. Fibrous organic textile material having distributed thereon anitrogenous phenolic resin prepared by reacting (A) phenol, (B)formaldehyde, (C) ammonium chloride and (D) sodium bisulnte in the molalratio of and a nitrogenous heterocyclic resin prepared by reacting (W)thiophene, (X) formaldehyde, (Y) ammonium chloride and (Z) sodiumbisulflte in the molal ratio 0! 1: a large excess of formaldehy deflfl.

7.-=;'l ?ibrous organic textile material having distribhted thereonsuccessively a nitrogenous phenolic resin prepared by reacting a phenol,formaldehyde and ammonium chloride and a nitrogenous heterocyclic. resinprepared by reacting a thiophene having at least one nuclear hydrogenatom of pronounced reactivity, formaldehyde and ammonium halide saidphenol, formaldehyde and said ammonium chloride having been reacted inthe molal ratio of 1:2 to

4:0.5-1 and said thiophene, formaldehyde and ammonium halide having beenreacted in the molal ratio of 1 to 2:05 to 4:025 to 3. JOHN W. SCHICK.HOWARD D. HARTOUGH.

REFERENCES man The following references are of record in the ille ofthis patent:

UNITED STATES PATEN'I'B Number Name 5 Date 2,114,121 Bender Apr. 12,1938

1. A METHOD OF CRUSH-PROOFING AND WATERPROOFING FIBROUS ORGANIC TEXTILEMATERIAL WHICH COMPRISES IMMERSING AN ORGANIC TEXTILE MATERIAL IN ANAQUEOUS BATH HAVING DISPERSED THEREIN ABOUT 10 TO ABOUT 15 PARTS BYWEIGHT OF A NITROGENOUS PHENOLIC RESIN PER 100 PARTS BY WEIGHT OFAQUEOUS MEDIUM. IMMERSING SAID ORGANIC TEXTILE MATERIAL IN AN AQUEOUS 12WEIGHT PER CENT FORMALDEHYDE SOLUTION, HEATING SAID ORGANIC TEXTILEMATERIAL AND SAID RESIN AT ABOUT 115 TO ABOUT 120* C., IMMERSING THESO-TREATED ORGANIC TEXTILE MATERIAL IN AN AQUEOUS ABOUT 3 TO ABOUT 25WEIGHT PER CENT SOLUTION OF A NITROGENOUS HETEROCYCLIC RESIN, IMMERSINGTHE SO-TREATED ORGANIC TEXTILE MATERIAL IN AN ALKALINE AQUEOUS SOLUTIONCONTAINING ABOUT 5 TO ABOUT 25 WEIGHT PER CENT FORMALDEHYDE, HEATING THESO-TRETED ORGANIC TEXTILE MATERIAL AT ABOUT 110 TO ABOUT 125* C. ANDWASHING THE SO-TREATED ORGANIC MATERIAL; SAID NITROGENOUS PHENOLIC RESINHAVING BEEN PREPARED BY REACTING (A) A PHENOL, (B) FORMALDEHYDE AND (C)A HALIDE SELECTED FROM THE GROUP CONSISTING OF HYDROHALIDES OF AMMONIAAND SUBSTITUTED AMMONIA IN THE MOLAL RATIO OF A:B:C=1:2-4:0.5-1; ANDSAID NITROGENOUS HETEROCYCLIC RESIN HAVING BEEN PREPARED BY REACTING (X)A COMPOUND HAVING AT LEAST ONE NUCLEAR HYDROGEN ATOM OF PRONOUNCEDREACTIVITY SELECTED FROM THE GROUP CONSISTING OF THIOPHENES, FURANS ANDPYRROLES, (Y) FORMALDEHYDE AND (Z) A HALIDE SELECTED FROM THE GROUPCONSISTING OF HALIDE OF AMMONIA AND SUBSTITUTED AMMONIA IN THE MOLALRATIO OF 1 TO 2:0.5 TO 4:0.25 TO 3.